Phase Change Inks

ABSTRACT

Phase change ink comprising carrier and colorant of formula 
     
       
         
         
             
             
         
       
     
     wherein R a  and R b  each, independently, are hydrogen, alkyl, including substituted and hetero-containing alkyl, aryl, including substituted and hetero-containing aryl, arylalkyl, including substituted and hetero-containing arylalkyl, or alkylaryl, including substituted and hetero-containing alkylaryl; R 1  and R 2  each, independently, are hydrogen, provided at least one of R 1  and R 2  is other than hydrogen, alkyl, including substituted and hetero-containing alkyl, aryl, including substituted and hetero-containing aryl, arylalkyl, including substituted and hetero-containing arylalkyl, or alkylaryl, including substituted and hetero-containing alkylaryl; R 3 , R 4 , R 5 , R 6 , and R 7  each, independently, are alkyl, including substituted and hetero-containing alkyl, aryl, including substituted and hetero-containing aryl, arylalkyl, including substituted and hetero-containing arylalkyl, alkylaryl, including substituted and hetero-containing alkylaryl, or a substituent other than hydrogen, alkyl, aryl, arylalkyl, or alkylaryl; wherein two or more of R 3 , R 4 , R 5 , R 6 , and R 7  can be joined together to form a ring.

CROSS-REFERENCE TO RELATED APPLICATIONS

Reference is made to U.S. Application No. (not yet assigned; Attorney Docket No. 20120980-US-NP), filed concurrently herewith, entitled “Colorant Compounds,” with the named inventors Jeffery H. Banning, Bo Wu, Nathan G. Starr, and Stephan V. Drappel, the disclosure of which is totally incorporated herein by reference.

Reference is made to U.S. Application No. (not yet assigned; Attorney Docket No. 20120986-US-NP), filed concurrently herewith, entitled “Dye Compound and Method of Making the Compound,” with the named inventors Jeffrey H. Banning, Bo Wu, Nathan Starr, and Stephan V. Drappel, the disclosure of which is totally incorporated herein by reference.

Reference is made to U.S. Application No. (not yet assigned; Attorney Docket No. 20120984-US-NP), filed concurrently herewith, entitled “Dye Compounds, Method of Making the Compounds and Ink Composition Employing the Compounds,” with the named inventors Jeffrey H. Banning, Jule W. Thomas, Jr., Bo Wu, and Stephan V. Drappel, the disclosure of which is totally incorporated herein by reference.

Reference is made to U.S. Application No. (not yet assigned; Attorney Docket No. 20120988-US-NP), filed concurrently herewith, entitled “Phase Change Inks Containing Wax-Soluble Near-Infrared Dyes,” with the named inventors Jeffrey H. Banning, Jule W. Thomas, Jr., Bo Wu, and Stephan V. Drappel, the disclosure of which is totally incorporated herein by reference.

BACKGROUND

Disclosed herein are phase change ink compositions. More specifically, disclosed herein are phase change inks containing colorant compounds particularly suitable for use in hot melt or phase change inks.

Many known colorant compounds are not soluble in phase change ink carriers. Further, pigment colorants, which are generally particulate in nature, as opposed to dye colorants, which are soluble in a selected carrier at the molecular level, can exhibit disadvantages such as settling of the pigment within the ink carrier, leading to difficulties such as clogging of the ink jet printhead. Accordingly, inks containing metal-free dye-based colorants that are soluble in the phase change ink carriers continue to be desirable.

SUMMARY

Disclosed herein is a phase change ink comprising: (I) a phase change ink carrier; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; (c) R₃, R₄, R₅, R₆, and R₇ each, independently of the others, are: (1) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl; (2) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (3) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; (4) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; or (5) a substituent other than hydrogen, alkyl, aryl, arylalkyl, or alkylaryl; wherein two or more of R₃, R₄, R₅, R₆, and R₇ can be joined together to form a ring. Also disclosed is a phase change ink composition comprising: (I) a phase change ink carrier; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 1 to about 100 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; (c) R₃, R₄, R₅, R₆, and R₇ each, independently of the others, are: (1) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 1 to about 100 carbons; (2) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (3) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; (4) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; or (5) a substituent other than hydrogen, alkyl, aryl, arylalkyl, or alkylaryl which is halogen, hydroxy, amino, imine, ammonium, pyridine, pyridinium, ether, aldehyde, ketone, ester, amide, carbonyl, thiocarbonyl, sulfate, sulfonate, sulfonic acid, sulfide, sulfoxide, phosphine, phosphonium, phosphate, phosphonate, nitrile, mercapto, nitro, nitroso, sulfone, acyl, acid anhydride, azide, azo, cyanato, isocyanato, thiocyanato, isothiocyanato, carboxylate, carboxylic acid, carbamate, carbamide, silyl, siloxyl, silane, or a combination thereof; wherein two or more of R₃, R₄, R₅, R₆, and R₇ can be joined together to form a ring. Further disclosed is a phase change ink composition comprising: (I) a phase change ink carrier comprising a branched triamide, a monoamide, a polyethylene wax, and a urethane resin; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; and (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 6 to about 100 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; wherein at least one of R₁ and R₂ has at least about 12 carbons.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a UV-visible spectrum of the material prepared in Example I, Part B.

FIG. 2 is a UV-visible spectrum of the material prepared in Example II.

DETAILED DESCRIPTION

The colorants disclosed herein are of the formulae

wherein:

(a) R_(a) and R_(b) each, independently of the other, are:

-   -   (i) hydrogen;     -   (ii) alkyl, including substituted and unsubstituted alkyl,         wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         alkyl, in one embodiment with at least about 1 carbon, in         another embodiment with at least about 6 carbons, in yet another         embodiment with at least about 12 carbons, and in still another         embodiment with at least about 16 carbons, and in one embodiment         with no more than about 100 carbons, in another embodiment with         no more than about 50 carbons, and in yet another embodiment         with no more than about 18 carbons;     -   (iii) aryl, including substituted and unsubstituted aryl,         wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         aryl, in one embodiment with at least about 4 carbons, in         another embodiment with at least about 5 carbons, and in yet         another embodiment with at least about 6 carbons, and in one         embodiment with no more than about 24 carbons, in another         embodiment with no more than about 18 carbons, and in yet         another embodiment with no more than about 12 carbons;     -   (iv) arylalkyl, including substituted and unsubstituted         arylalkyl, wherein the alkyl portion of arylalkyl can be linear         or branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of arylalkyl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment at least about 7 carbons, and in         one embodiment no more than about 100 carbons, in another         embodiment no more than about 50 carbons, and in yet another         embodiment no more than about 18 carbons, such as benzyl or the         like; or     -   alkylaryl, including substituted and unsubstituted alkylaryl,         wherein the alkyl portion of alkylaryl can be linear or         branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of alkylaryl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment at least about 7 carbons, and in         one embodiment no more than about 100 carbons, in another         embodiment no more than about 50 carbons, and in yet another         embodiment no more than about 18 carbons, such as tolyl or the         like;

(b) R₁ and R₂ each, independently of the other, are:

-   -   (i) hydrogen, provided that at least one of R₁ and R₂ is other         than hydrogen;     -   (ii) alkyl, including substituted and unsubstituted alkyl,         wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         alkyl, in one embodiment with at least about 6 carbons, in         another embodiment with at least about 12 carbons, and in yet         another embodiment with at least about 16 carbons, and in one         embodiment with no more than about 100 carbons, in another         embodiment with no more than about 50 carbons, and in yet         another embodiment with no more than about 18 carbons, provided         that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has         in one embodiment at least about 6 carbons, in another         embodiment at least about 12 carbons, and in yet another         embodiment at least about 16 carbons;     -   (iii) aryl, including substituted and unsubstituted aryl,         wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         aryl, in one embodiment with at least about 4 carbons, in         another embodiment with at least about 5 carbons, and in yet         another embodiment with at least about 6 carbons, and in one         embodiment with no more than about 24 carbons, in another         embodiment with no more than about 18 carbons, and in yet         another embodiment with no more than about 12 carbons;     -   (iv) arylalkyl, including substituted and unsubstituted         arylalkyl, wherein the alkyl portion of arylalkyl can be linear         or branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of arylalkyl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment at least about 7 carbons, and in         one embodiment no more than about 100 carbons, in another         embodiment no more than about 50 carbons, and in yet another         embodiment no more than about 18 carbons, such as benzyl or the         like; or     -   alkylaryl, including substituted and unsubstituted alkylaryl,         wherein the alkyl portion of alkylaryl can be linear or         branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of alkylaryl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment at least about 7 carbons, and in         one embodiment no more than about 100 carbons, in another         embodiment no more than about 50 carbons, and in yet another         embodiment no more than about 18 carbons, such as tolyl or the         like; and

(c) R₃, R₄, R₅, R₆, and R₇ each, independently of the others, are:

-   -   (1) hydrogen;     -   (2) alkyl, including substituted and unsubstituted alkyl,         wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         alkyl, in one embodiment with at least about 1 carbon, in         another embodiment with at least about 6 carbons, and in yet         another embodiment with at least about 12 carbons, and in one         embodiment with no more than about 100 carbons, in another         embodiment with no more than about 50 carbons, and in yet         another embodiment no more than about 18 carbons;     -   (3) aryl, including substituted and unsubstituted aryl, wherein         hetero atoms, such as oxygen, nitrogen, sulfur, silicon,         phosphorus, boron, or the like, may optionally be present in         aryl, in one embodiment with at least about 4 carbons, in         another embodiment with at least about 5 carbons, and in yet         another embodiment with at least about 6 carbons, and in one         embodiment with no more than about 24 carbons, in another         embodiment with no more than about 18 carbons, and in yet         another embodiment no more than about 12 carbons;     -   (4) arylalkyl, including substituted and unsubstituted         arylalkyl, wherein the alkyl portion of arylalkyl can be linear         or branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of arylalkyl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment with at least about 7 carbons, and         in one embodiment with no more than about 100 carbons, in         another embodiment with no more than about 50 carbons, and in         yet another embodiment no more than about 18 carbons, such as         benzyl or the like;     -   (5) alkylaryl, including substituted and unsubstituted         alkylaryl, wherein the alkyl portion of alkylaryl can be linear         or branched, saturated or unsaturated, cyclic or acyclic, and         substituted or unsubstituted, wherein hetero atoms, such as         oxygen, nitrogen, sulfur, silicon, phosphorus, boron, or the         like, may optionally be present in either the aryl or the alkyl         portion of alkylaryl, in one embodiment with at least about 5         carbons, in another embodiment with at least about 6 carbons,         and in yet another embodiment with at least about 7 carbons, and         in one embodiment with no more than about 100 carbons, in         another embodiment with no more than about 50 carbons, and in         yet another embodiment no more than about 18 carbons, such as         tolyl or the like; or     -   (6) a substituent, examples of which include (A) halogen,         including fluorine, chlorine, bromine, and iodine; (B)         hydroxy; (C) primary, secondary, and/or tertiary amino; (D)         imine; (E) ammonium; (F) pyridine; (G) pyridinium; (H)         ether; (I) aldehyde; (J) ketone; (K) ester; (L) amide; (M)         carbonyl; (N) thiocarbonyl; (O) sulfate; (P) sulfonate; (Q)         sulfonic acid; (R) sulfide; (S) sulfoxide; (T) phosphine; (U)         phosphonium; (V) phosphate; (W) phosphonate; (X) nitrile; (Y)         mercapto; (Z) nitro; (AA) nitroso; (BB) sulfone; (CC) acyl; (DD)         acid anhydride; (EE) azide; (FF) azo; (GG) cyanato; (HH)         isocycanato; (II) thiocyanato; (JJ) isothiocyanato; (KK)         carboxylate; (LL) carboxylic acid; (MM) urethane (carbamate);         (NN) urea (carbamide); (OO) silyl; (PP) siloxyl; (QQ) silane; or         the like, as well as combinations or mixtures thereof;

wherein two or more of R₃, R₄, R₅, R₆, and R₇ can be joined together to form a ring;

wherein examples of the substituents which may or may not be present on the substituted alkyl, aryl, arylalkyl, or alkylaryl groups include the same as those listed as (A) through (QQ) or the like, as well as combinations or mixtures thereof.

For example, when R₃, R₄, and R₆ are hydrogen, R₇ is chlorine, and R₅ is sulfone linked to methyl, the compound has the formula

When R₃ and R₄ are hydrogen, R₅ is azo linked to phenyl, and R₆ and R₇ are linked to form an aromatic ring, the compound has the formula

Similarly, when R₄ and R₅ are hydrogen, R₃ is azo linked to phenyl, and R₆ and R₇ are linked to form an aromatic ring, the compound has the formula

Specific examples of suitable R₁ and R₂ groups include:

-n-C_(n)H_(2n+1)

wherein n is from about 8 to about 100, such as

wherein m+p is from about 8 to about 100, such as

wherein q+r is from about 8 to about 100,

wherein s+t is from about 8 to about 100, such as

wherein t is 11, 17, 21, 27, 37 or 47;

wherein u+v is from about 8 to about 100,

wherein w+x is from about 8 to about 100,

wherein y+z is from about 8 to about 100,

wherein e+f is from about 8 to about 100, or the like, as well as combinations or mixtures thereof.

Compounds having the

basic structures can be prepared by methods analogous to those disclosed in, for example, U. Pfüller, H. Franz, and A. Preiss, Histochemistry 54, 237-250 (1977), the disclosure of which is totally incorporated herein by reference. This method can also be used to prepare analogous compounds of the general generic formulae

such as compounds of the formulae

Alternatively, the compounds can be prepared by first obtaining a “coupler” of the formula

and reacting it with an aromatic amine of the formula

in the presence of nitrous acid or another reagent that generates nitrous acid in situ, such as nitrosylsulfuric acid, a NO₂— salt (such as NaNO₂ or KNO₂) in combination with a strong mineral acid (such as HCl or the like), or the like, as follows:

Coupler compounds having the desired R₁ and R₂ groups can be prepared by reacting 1,8-diaminonaphthalene with the appropriate ketone. For example, the reaction with stearone yields R₁ and R₂ both being —(CH₂)₁₇CH₃:

Incorporating functional groups into the ketone allows further reaction of the R₁ and R₂ groups subsequent to formation of the coupler. For example, when the ketone is dihydroxyacetone, the coupler is of the formula

Further reaction of this compound can create acid, ester, amide, carbamate, or like compounds by known methods.

Alternatively, the coupler compound can be prepared by a transesterification process as follows:

using a simple starting material such as diethyl mesoxalate, available from Aldrich Chemical Co., Milwaukee, Wis.

The colorant is present in the ink in any desired or effective amount to obtain the desired color or hue, in one embodiment of at least about 0.1% by weight of the ink, in another embodiment of at least about 0.5% by weight of the ink, in yet another embodiment of at least about 1% by weight of the ink, in still another embodiment of at least about 2% by weight of the ink, and in another embodiment of at least about 3% by weight of the ink, and in one embodiment of no more than about 20% by weight of the ink, in another embodiment of no more than about 13% by weight of the ink, and in yet another embodiment of no more than about 10% by weight of the ink. The colorant as disclosed herein can either be the sole colorant in the ink or can be present in combination with other colorants.

The inks disclosed herein contain a phase change ink carrier in addition to the colorant. Any desired or effective carrier composition can be used. Examples of suitable ink carrier materials include fatty amides, such as monoamides, triamides, tetra-amides, mixtures thereof, or the like. Specific examples of suitable fatty amide ink carrier materials include stearyl stearamide, a dimer acid based tetra-amide that is the reaction product of dimer acid, ethylene diamine, and stearic acid, a dimer acid based tetra-amide that is the reaction product of dimer acid, ethylene diamine, and a carboxylic acid having at least about 36 carbon atoms, or the like, as well as mixtures thereof. When the fatty amide ink carrier is a dimer acid based tetra-amide that is the reaction product of dimer acid, ethylene diamine, and a carboxylic acid having at least about 36 carbon atoms, the carboxylic acid is of the general formula

wherein R is an alkyl group, including linear, branched, saturated, unsaturated, and cyclic alkyl groups, said alkyl group in one embodiment having at least about 36 carbon atoms, in another embodiment having at least about 40 carbon atoms, said alkyl group in one embodiment having no more than about 200 carbon atoms, in another embodiment having no more than about 150 carbon atoms, and in yet another embodiment having no more than about 100 carbon atoms. Carboxylic acids of this formula are commercially available from, for example, Baker Petrolite, Tulsa, Okla., and can also be prepared as described in Example 1 of U.S. Pat. No. 6,174,937, the disclosure of which is totally incorporated herein by reference. Further information on fatty amide carrier materials is disclosed in, for example, U.S. Pat. No. 4,889,560, U.S. Pat. No. 4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No. 4,830,671, U.S. Pat. No. 6,174,937, U.S. Pat. No. 5,372,852, U.S. Pat. No. 5,597,856, U.S. Pat. No. 6,174,937, and British Patent GB 2 238 792, the disclosures of each of which are totally incorporated herein by reference. Also suitable are branched triamides as disclosed in U.S. Pat. No. 6,860,930, the disclosure of which is totally incorporated herein by reference. In one specific embodiment, the branched triamide is of the formula

wherein x, y, and z each independently represent the number of propyleneoxy repeat units and x+y+z is from about 5 to about 6, and wherein p, q, and r are integers representing the number of repeat —(CH₂)— units, wherein p, q, and r each, independently of the others, are from about 34 to about 40.

Also suitable as phase change ink carrier materials are isocyanate-derived resins and waxes, such as urethane isocyanate-derived materials, urea isocyanate-derived materials, urethane/urea isocyanate-derived materials, mixtures thereof, or the like. Further information on isocyanate-derived carrier materials is disclosed in, for example, U.S. Pat. No. 5,750,604, U.S. Pat. No. 5,780,528, U.S. Pat. No. 5,782,966, U.S. Pat. No. 5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat. No. 5,830,942, U.S. Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S. Pat. No. 6,309,453, British Patent GB 2 294 939, British Patent GB 2 305 928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCT Publication WO 94/14902, PCT Publication WO 97/12003, PCT Publication WO 97/13816, PCT Publication WO 96/14364, PCT Publication WO 97/33943, and PCT Publication WO 95/04760, the disclosures of each of which are totally incorporated herein by reference.

Mixtures of fatty amide materials and isocyanate-derived materials can also be employed as the ink carrier composition.

Additional suitable phase change ink carrier materials include paraffins, microcrystalline waxes, polyethylene waxes, ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides and other waxy materials, sulfonamide materials, resinous materials made from different natural sources (such as, for example, tall oil rosins and rosin esters), and many synthetic resins, oligomers, polymers and copolymers, such as ethylene/vinyl acetate copolymers, ethylene/acrylic acid copolymers, ethylene/vinyl acetate/acrylic acid copolymers, copolymers of acrylic acid with polyamides, or the like, ionomers, or the like, as well as mixtures thereof. One or more of these materials can also be employed in a mixture with a fatty amide material and/or an isocyanate-derived material.

Specific examples of suitable waxes include polyethylene waxes such as PE 500 and PE 655, available from Baker Petrolite, Tulsa, Okla., Fischer-Tropsch waxes, available from Sasol Wax Americas, Inc., Shelton, Conn., waxes as disclosed in, for example, U.S. Patent Publications 20060257495 and 2005/0130054, the disclosures of which are totally incorporated herein by reference, and waxes as disclosed in U.S. Pat. Nos. 7,407,539, 7,377,971, 7,381,254, 7,311,768, and 7,658,486, the disclosures of each of which are totally incorporated herein by reference.

Also suitable are ink carriers comprising crystalline-amorphous mixtures, such as those disclosed in, for example, U.S. Patent Publications 20120274699, 20120274710, 20120272859, 20120272861, 20120274716, 20120272862, 20120272860, 20120272865, 20120272863, 20120272864, 20120274700, 20120277462, and 20120274698, and Copending application Ser. Nos. 13/196,157, 13/680,271, and 13/196,227, the disclosures of each of which are totally incorporated herein by reference, or the like. Examples of suitable amorphous materials include oxazolines and oxazoline derivatives, esters of citric acid, isosorbide oligomers, polyterpene resins, amorphous rosins and rosin esters, or the like, as well as mixtures thereof. Examples of suitable crystalline materials include those disclosed in U.S. Pat. No. 6,682,587, the disclosure of which is totally incorporated herein by reference, crystalline aromatic monoesters, crystalline diesters, crystalline esters of tartaric acid, crystalline aromatic amides, crystalline oxazolines, trans-cinnamic diesters, or the like, as well as mixtures thereof.

The ink carrier (defined as all of the ink components other than the colorant) is present in the phase change ink in any desired or effective amount, in one embodiment of at least about 0.1% by weight of the ink, in another embodiment of at least about 50% by weight of the ink, and in yet another embodiment of at least about 90% by weight of the ink, and in one embodiment of no more than about 99% by weight of the ink, in another embodiment of no more than about 98% by weight of the ink, and in yet another embodiment of no more than about 95% by weight of the ink.

The inks can also optionally contain an antioxidant. The optional antioxidants of the ink compositions protect the images from oxidation and also protect the ink components from oxidation during the heating portion of the ink preparation process. Specific examples of suitable antioxidants include NAUGUARD® 524, NAUGUARD® 76, and NAUGUARD® 512 (commercially available from Uniroyal Chemical Company, Oxford, Conn.), IRGANOX® 1010 (commercially available from Ciba Geigy), or the like. When present, the optional antioxidant is present in the ink in any desired or effective amount, in one embodiment of at least about 0.01% by weight of the ink, in another embodiment of at least about 0.1% by weight of the ink, and in yet another embodiment of at least about 1% by weight of the ink, and in one embodiment of no more than about 20% by weight of the ink, in another embodiment of no more than about 5% by weight of the ink, and in yet another embodiment of no more than about 3% by weight of the ink.

Other optional additives to the inks include clarifiers, such as UNION CAMP® X37-523-235 (commercially available from Union Camp), in an amount in one embodiment of at least about 0.01% by weight of the ink, in another embodiment of at least about 0.1% by weight of the ink, and in yet another embodiment of at least about 5% by weight of the ink, and in one embodiment of no more than about 98% by weight of the ink, in another embodiment of no more than about 50% by weight of the ink, and in yet another embodiment of no more than about 10% by weight of the ink, tackifiers, such as FORAL® 85, a glycerol ester of hydrogenated abietic (rosin) acid (commercially available from Hercules), FORAL® 105, a pentaerythritol ester of hydroabietic (rosin) acid (commercially available from Hercules), CELLOLYN® 21, a hydroabietic (rosin) alcohol ester of phthalic acid (commercially available from Hercules), ARAKAWA KE-311 and KE-100 Resins, triglycerides of hydrogenated abietic (rosin) acid (commercially available from Arakawa Chemical Industries, Ltd.), synthetic polyterpene resins such as NEVTAC® 2300, NEVTAC® 100, and NEVTAC® 80 (commercially available from Neville Chemical Company), WINGTACK® 86, a modified synthetic polyterpene resin (commercially available from Goodyear), or the like, in an amount in one embodiment of at least about 0.1% by weight of the ink, in another embodiment of at least about 5% by weight of the ink, and in yet another embodiment of at least about 10% by weight of the ink, and in one embodiment of no more than about 98% by weight of the ink, in another embodiment of no more than about 75% by weight of the ink, and in yet another embodiment of no more than about 50% by weight of the ink, adhesives, such as VERSAMID® 757, 759, or 744 (commercially available from Henkel), in an amount in one embodiment of at least about 0.1% by weight of the ink, in another embodiment of at least about 1% by weight of the ink, and in yet another embodiment of at least about 5% by weight of the ink, and in one embodiment of no more than about 98% by weight of the ink, in another embodiment of no more than about 50% by weight of the ink, and in yet another embodiment of no more than about 10% by weight of the ink, plasticizers, such as UNIPLEX® 250 (commercially available from Uniplex), the phthalate ester plasticizers commercially available from Monsanto under the trade name SANTICIZER®, such as dioctyl phthalate, diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER® 278), triphenyl phosphate (commercially available from Monsanto), KP-140®, a tributoxyethyl phosphate (commercially available from FMC Corporation), MORFLEX® 150, a dicyclohexyl phthalate (commercially available from Morflex Chemical Company Inc.), trioctyl trimellitate (commercially available from Eastman Kodak Co.), or the like, in an amount in one embodiment of at least about 0.1% by weight of the ink, in another embodiment of at least about 1% by weight of the ink, and in yet another embodiment of at least about 2% by weight of the ink, and in one embodiment of no more than about 50% by weight of the ink, in another embodiment of no more than about 30% by weight of the ink, and in yet another embodiment of no more than about 10% by weight of the ink, or the like.

The inks disclosed herein are phase change inks. By this is meant that they are solids at a temperature of about 25° C. and are liquids when melted at temperatures of at least about 40° C. or higher.

The ink compositions in one embodiment have peak melting points of no lower than about 50° C., in another embodiment of no lower than about 60° C., and in yet another embodiment of no lower than about 70° C., and have peak melting points in one embodiment of no higher than about 160° C., in another embodiment of no higher than about 140° C., and in yet another embodiment of no higher than about 100° C.

The ink compositions in one embodiment have onset melting points of no lower than about 50° C., in another embodiment of no lower than about 52° C., and in yet another embodiment of no lower than about 55° C., and have onset melting points in one embodiment of no higher than about 75° C., in another embodiment of no higher than about 72° C., and in yet another embodiment of no higher than about 69° C.

The ink compositions generally have melt viscosities at the jetting temperature (in one embodiment no lower than about 75° C., in another embodiment no lower than about 85° C., and in yet another embodiment no lower than about 95° C., and in one embodiment no higher than about 150° C., and in another embodiment no higher than about 120° C.) in one embodiment of no more than about 30 centipoise (cps), in another embodiment of no more than about 20 cps, and in yet another embodiment of no more than about 15 cps, and in one embodiment of no less than about 2 cps, in another embodiment of no less than about 5 cps, and in yet another embodiment of no less than about 7 cps. In another specific embodiment, the inks have viscosities of from about 7 to about 15 cps at temperatures of about 110, 115, and/or 120° C.

Specific embodiments will now be described in detail. These examples are intended to be illustrative, and the claims are not limited to the materials, conditions, or process parameters set forth in these embodiments. All parts and percentages are by weight unless otherwise indicated.

Example I A. Preparation of 2,3-dihydro-2,2-distearylperimidine

To a 1,000 mL 3-necked 24/40 round-bottom flask with stoppers on two of the necks, a Dean-Stark trap with condenser on the center neck, and a TEFLON coated stir magnet was charged 80 g stearone (obtained from Witco Chemical Co.), 27.5 g 1,8-diaminonaphthalene (purified following the procedure of H. O. House et al., J. Org Chem. 1972, 37 7, p. 1003), representing a slight excess), 0.1 g p-toluene sulfonic acid (obtained from Aldrich Chemical Co.), and 170 g toluene. The reaction vessel was placed in a 130° C. silicone oil bath and allowed to reflux for 16 h. Water was collected with toluene in the DS-trap. Thin Layer Chromatography (normal phase silica with toluene as the mobile phase) was then run on the reaction product. No starting stearone was observed, but some 1,8-diaminonaphthalene was observed as it was run in excess. The reaction mixture was then poured into a 1 L beaker with 400 mL methanol and allowed to stir. The solid product was then collected via vacuum filtration and a Buchner funnel and the solid collected was allowed to dry. TLC (normal phase silica with toluene as the mobile phase) was then run on the purified product and no stearone or 1,8-diaminonaphthalene were observed. An IR spectrum of the product was run and the peaks corresponded to 2,3-dihydro-2,2-distearylperimidine.

B. Dye Preparation

To a 250 mL beaker equipped with a TEFLON coated stir magnet was charged 130 g of a mixture of 5 parts acidic acid and 1 part propionic acid, 1.74 g concentrated HCl, and 5 g 4-phenylazo-1-naphthylamine HCl (obtained from Aldrich Chemical Co.). The reaction mixture was stirred at room temperature for 20 min. The contents turned purple and the solid did not totally dissolve. The beaker was then chilled in an ice/salt bath to 0-5° C. More solids came out upon cooling and the content became thick. With hand stirring, 1.33 g sodium nitrite/15 mL water solution was added dropwise. No exotherm was observed but the contents turned yellow and all solids dissolved. A PMA test to determine if excess NO⁺ has been killed off before coupling (as described in U.S. Pat. No. 7,812,140, the disclosure of which is totally incorporated herein by reference) was done after one hour of stirring at 0-5° C., which was positive. Then the cold diazonium salt solution was slowly poured into the 250 mL beaker containing 11.2 g of the waxy perimidine coupler prepared as described in Part A above and 90 g THF. A dark blue precipitate began to form, eventually resulting in a sticky solid clump. The brown liquid was decanted and discarded. The clumpy solids were dissolved in 200 mL toluene, transferred to a separatory funnel, and washed three times with water, followed by a single 150 mL water/100 mL methanol wash. The toluene in the top layer was evaporated and dried in a vacuum oven. The spectral strength of the recovered product in toluene was 24311 mIA/g @576 nm, and 12019 mIA/g @423 nm. The UV-visible spectrum of this material, taken on a Perkin Elmer Lambda 2S UV/Vis spectrophotometer, is shown in FIG. 1.

Example II

To a 50 mL flask equipped with TEFLON coated magnetic stir was charged 10.6 g water and 8.04 g conc. H₂SO₄. With stirring, 3 g 2-chloro-4-(methylsulfonyl) benzamine (CAMSU) (MW=205.5, obtained from Clarient Chemical Corp.) was added and formed a white slurry. The jar was then placed in an ice bath and allowed to cool to 0° C., after which 4.87 g nitrosylsulfuric acid (40% in H₂SO₄, MW=127, obtained from Aldrich Chemical Co.) was added slowly to keep T<0° C. The contents turned to a clear yellow solution. To a separate 500 mL beaker was charged 9.4 g of a perimidine coupler prepared as described in Part A of Example I and 70 g isopropanol. The contents dissolved upon heating. Thereafter 3 g conc. H₂SO₄ was added. The clear solution in the jar was poured into the perimidine coupler solution. A dark yellow very tacky solid formed. The pH was adjusted >7 by addition of 40% NaOH solution. Then the contents were poured into a separatory funnel. The lower water layer was discarded. Toluene was added to dissolve the top tacky solid layer. Then the red purple toluene layer was washed with 2× water. The solvent was then evaporated and the solid collected. A spectral strength (UV-Vis spectrum) was run on the sample and is shown in FIG. 2. The structure of the sample was believed to be that of the azo-perimidine shown above.

Example III Part A: Preparation of 2,3-dihydro-2,2-distearylperimidine

To a 100 mL flask with TEFLON-coated stir magnet was added 33.4 g 4-hydroxy-2-butanone and 20 g 1,8-diaminonaphthalene. The reaction vessel was placed in a silicone oil bath at 70° C. and stirring was initiated. After 3 h a sample was taken and Thin Layer Chromatography (normal phase silica with 90/10 MeOH/toluene mobile phase) was then run on the reaction product, and no starting reactants were observed. The reaction product was poured into a 1 L beaker with 300 mL deionized water. The solids precipitated out and were collected via vacuum filtration in a Buchner funnel and allowed to dry in a vacuum oven. An IR spectrum of the product was run and the peaks corresponded to the expected product 2,3-dihydro-2-methyl-2-hydroxyethylperimidine. About 24.9 g of product were obtained representing 86% yield.

Part B: Dye Preparation

To a 250 mL beaker equipped with a TEFLON coated stir magnet is charged 130 g of a mixture of 5 parts acetic acid and 1 part propionic acid, 1.74 g concentrated HCl, and 5 g 4-phenylazo-1-naphthylamine HCl (obtained from Aldrich Chemical Co.). The reaction mixture is stirred at room temperature for 20 min. The contents turn purple and the solid does not totally dissolve. The beaker is then chilled in an ice/salt bath to 0-5° C. More solids come out upon cooling and the contents become thick. With hand stirring, 1.33 g sodium nitrite/15 mL water solution is added dropwise. No exotherm is observed but the contents turn yellow and all solids dissolve. After one hour of stirring at 0-5° C., the cold diazonium salt solution is slowly poured into the 250 mL beaker containing 11.2 g of the hydroxyl containing perimidine coupler prepared as described in Part A above and 90 g THF. The precipitate that is formed is collected and is dissolved in 200 mL CH₂Cl₂, transferred to a separatory funnel, and washed three times with water. The CH₂Cl₂ from the bottom layer is evaporated and the solids are dried in a vacuum oven.

Part C: Urethane Preparation

To a 250 mL 1-necked round bottom flask equipped with a TEFLON coated stir magnet, condenser, and 130° C. oil bath is charged 150 g toluene (obtained from J. T. Baker Chemical Co.), 10.0 g of the hydroxyethyl pyrimidine bis-azo dye from Part B above, and 6.1 g octadecyl isocyanate (Aldrich Chemical Co.). The reaction mixture is stirred while placed in the oil bath and 2 drops of dibutyltindilaurate (catalyst) is added. The reaction flask is refluxed for 6 h. A sample is removed and an FTIR spectrum run to follow the disappearance of the isocyanate peak (found at about 2230 cm⁻¹). When no isocyanate peak is observed, the toluene is distilled off, leaving a waxy molten sold. The molten solid product is decanted into an aluminum tin and allowed to solidify.

Part D: Ester Preparation

To a 250 mL 1-necked round-bottom flask equipped with a TEFLON coated stir magnet, condenser with Dean-Stark trap, and 150° C. oil bath is charged 150 g toluene, 10.0 g of the hydroxyethyl pyrimidine from Part B above, and 6.0 g octadecanoic acid (Aldrich Chemical Co). The reaction mixture is stirred and placed in the oil bath and a spatula tip of p-toluene sulfonic acid (catalyst) is added. The reaction flask is refluxed for 16 h. A sample is removed and an FTIR spectrum run to follow the appearance of the carbonyl peak (found at about 1700 cm⁻¹). When the reaction is complete, the toluene is distilled off leaving a waxy molten sold. The molten solid product is decanted into an aluminum tin and allowed to solidify.

Example IV Part A: Preparation of 2,3-dihydro-2,2-carboxyethylperimidine

To a 250 mL 1-neck round-bottom flask equipped with a TEFLON-coated stir magnet and condenser is added 17.4 g diethyl mesoxalate, 15.8 g 1,8-diaminonaphthalene, and 125 mL toluene. The reaction vessel Is placed in a silicone oil bath at 70° C. and stirring is initiated. After about 3 h a sample is taken and TLC (normal phase silica with 90/10 MeOH/toluene as the mobile phase) is then run on the reaction product to determine that no starting reactants remain. When the reaction is complete, the toluene is distilled off leaving a waxy molten sold. The molten solid is decanted into an aluminum tin and allowed to solidify.

Part B: Preparation of 2,3-dihydro-2,2-biscarboxyunilin(700)perimidine

To a 500 mL 1-neck round-bottom flask equipped with a TEFLON coated stir magnet and condenser with Dean-Stark trap are added 31.4 g 2,3-dihydro-2,2-carboxyethylperimidine (as prepared in Part A of this Example), 54 g octadecylamine (Aldrich Chemical Co.), and 250 mL toluene. The flask is placed in a 150° C. oil bath and refluxed until TLC (normal phase silica with 90/10 MeOH/toluene as the mobile phase) indicates no starting reactant remains. When the reaction is completed, the toluene is distilled off leaving a waxy molten sold. The molten solid is poured into an aluminum tin and allowed to solidify.

Part C: Dye Preparation

To a 250 mL beaker equipped with TEFLON coated stir magnet is charged 130 g of a mixture of 5 parts acetic acid and 1 part propionic acid, 1.74 g concentrated HCl, and 5 g 4-phenylazo-1-naphthylamine HCl. The reaction mixture is stirred at room temperature for 20 min. The contents turn purple and the solid does not totally dissolve. The beaker is then chilled in an ice/salt bath to 0-5° C. More solids come out upon cooling and the contents become thick. With hand stirring, a 1.33 g sodium nitrite/15 mL water solution is added dropwise. No exotherm is observed but the contents turn yellow and all solids dissolve. After one hour of stirring at 0-5° C., the cold diazonium salt solution is slowly poured into the 250 mL beaker containing 34.7 g of the diester containing perimidine coupler prepared as described in Part B of this Example and 90 g tetrahydrofuran. The precipitate formed is collected and dissolved in 200 mL toluene, transferred to a separatory funnel, and washed three times with water. The toluene layer is collected and transferred to a 500 mL round-bottom flask with TEFLON coated magnet and distillation column attached, the toluene distilled off, and the molten black dye collected in aluminum tins and allowed to cool-solidify.

Example V Part A: Preparation of 2,3-dihydro-2,2-biscarboxystearylamideperimidine

To a 500 mL 1-neck round-bottom flask equipped with a TEFLON coated stir magnet and condenser with Dean-Stark trap is added 31.4 g 2,3-dihydro-2,2-carboxyethylperimidine (prepared as described in Example IV, part A), 54 g octadecylamine (Aldrich Chemical Corp), and 250 mL toluene. The flask is placed in a 150° C. oil bath and refluxed until TLC (normal phase silica with 90/10 MeOH/toluene as the mobile phase) indicates no starting reactant remains. When the reaction is complete, the toluene is distilled off leaving a waxy molten sold. The molten solid is decanted into aluminum tins and allowed to solidify.

Part B: Dye Preparation

To a 250 mL beaker equipped with TEFLON coated stir magnet is charged 130 g of a mixture of 5 parts acetic acid and 1 part propionic acid, 1.74 g concentrated HCl, and 5 g 4-phenylazo-1-naphthylamine HCl (obtained from Aldrich Chemical Co.). The reaction mixture is stirred at room temperature for 20 min. The contents turn purple and the solid does not totally dissolve. The beaker is then chilled in an ice/salt bath to 0-5° C. More solids come out upon cooling and the contents become thick. With hand stirring, 1.33 g sodium nitrite/15 mL water solution is added dropwise. No exotherm is observed but the contents turn yellow and all solids dissolve. After one hour of stirring at 0-5° C., the cold diazonium salt solution is slowly poured into the 250 mL beaker containing 15.4 g of the diamide-containing perimidine coupler prepared as described in Part A of this Example and 90 g tetrahydrofuran. The precipitate formed is collected and dissolved in 200 mL toluene, transferred to a separatory funnel, and washed three times with water. The toluene layer is collected and transferred to a 500 mL round bottom flask with TEFLON coated magnet and distillation column attached, the toluene distilled off, and the molten black dye collected in aluminum tins and allowed to cool-solidify.

Example VI Solubility Testing

Solvent Black 3, of the formula

molecular weight 456, and the distearyl derivative, a compound as disclosed herein, of the formula

molecular weight 892, were compared for solubility in polyethylene wax, a predominant component in phase change inks. 1 g of the Solvent Black 3 and 2 g of the distearyl derivative (because its molecular weight was about twice that of Solvent Black 3) were each dissolved in 50 g portions of POLYWAX 655 (Baker Petrolite) in 100 mL beakers equipped with magnetic stir bars. The solutions were placed in 120° C. oil baths and allowed to stir for 3 h, followed by cessation of stirring for 1 h, after which the solutions were poured into aluminum tins. At this time, a substantial amount of the Solvent Black 3 appeared on the bottom of its beaker, whereas almost no solids appeared on the bottom of the beaker containing the distearyl derivative.

The two compositions (“inks” were applied to paper using a RK Print-Coat Instruments Ltd. K-proofer. Had all of the solids dissolved in both portions of the polyethylene wax, identical optical densities would have been expected. The composition containing the distearyl derivative, however, yielded images that were considerably darker than those generated with the composition containing Solvent Black 3.

Ink Example 1

An ink base was prepared by melting, mixing, and filtering the following ingredients:

polyethylene wax (PE500, Baker Petrolite, Tulsa, Okla., CH₃(CH₂)₃₆CH₃), 50 parts by weight;

stearyl stearamide wax (KEMAMIDE® S-180, Crompton Corporation, Greenwich, Conn.), 15 parts by weight;

triamide resin obtained from reaction of three equivalents UNICID® 700 (long chain hydrocarbon having a terminal carboxylic acid group; Baker Petrolite, Tulsa, Okla.) with one equivalent JEFFAMINE T-403 (Huntsman Corp.) (triamide prepared as described in Example 2 of U.S. Pat. No. 6,860,930), 15 parts by weight;

rosin ester resin obtained from reaction of three equivalents abietic acid and 1 mole glycerin (Arakawa Chem), 15 parts by weight;

urethane resin, adduct of three equivalents stearyl isocyanate and a glycerol-based propoxylated alcohol (prepared as described in Example 4 of U.S. Pat. No. 6,309,453, 5 parts by weight;

NAUGUARD® 445 antioxidant (Uniroyal Chemical Co., Middlebury, Conn.), 0.20 parts by weight.

Thereafter, 600 g of these components were added to a 1 L beaker and heated in an oven at 135° C. until molten. Subsequently, the beaker was inserted into a heating mantle set to 135° C. and the contents of the beaker were stirred for 45 min. The resulting ink was then filtered through a combination of WHATMAN #3 and 0.2 μm NAE filters and placed in a Mott filter assembly. Filtration was supported by the addition of 1% by weight FILTER AID, Fluka Chemika, Switzerland, and proceeded at 135° C. until complete after 6 h. The ink base was poured into molds containing 31 g of the colorless ink base and allowed to cool.

About 30 g of the colorless ink base thus prepared was placed in a 100 mL beaker with a magnetic stir bar and subsequently placed in a 135° C. oil bath until molten. About 0.5 g of the dye from Example I was then added and stirred for about 3 h. The resulting black colored ink was then poured into an aluminum mold.

Ink Example 2

About 30 g of the colorless ink base prepared in Ink Example 1 was placed in a 100 mL beaker with a magnetic stir bar and subsequently placed in a 135° C. oil bath until molten. About 0.5 g of the dye from Example II was then added and stirred for about 3 h. The resulting bluish-black colored ink was then poured into an aluminum mold.

Ink Testing

Using a RK Print-Coat Instruments Ltd. K-proofer, print samples of the inks from Ink Examples 1 and 2 were produced on XEROX® 4200 paper at 130° C. These proofs showed three different intensities of ink coverage on the paper for each ink, with the different intensities corresponding to three different depths of gravure recesses on the gravure type plates used in the K-proofer. The prints with the Ink of Example 1 gave black prints. The prints with the Ink of Example 2 gave bluish prints.

Other embodiments and modifications of the present invention may occur to those of ordinary skill in the art subsequent to a review of the information presented herein; these embodiments and modifications, as well as equivalents thereof, are also included within the scope of this invention.

The recited order of processing elements or sequences, or the use of numbers, letters, or other designations therefor, is not intended to limit a claimed process to any order except as specified in the claim itself. 

What is claimed is:
 1. A phase change ink comprising: (I) a phase change ink carrier; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; (c) R₃, R₄, R₅, R₆, and R₇ each, independently of the others, are: (1) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl; (2) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl; (3) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl; (4) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl; or (5) a substituent other than hydrogen, alkyl, aryl, arylalkyl, or alkylaryl; wherein two or more of R₃, R₄, R₅, R₆, and R₇ can be joined together to form a ring.
 2. An ink according to claim 1 wherein the colorant compound is of the formula


3. An ink according to claim 1 wherein the colorant compound is of the formula


4. An ink according to claim 1 wherein at least one of R₁ and R₂ is of the formula: -n-C_(n)H_(2n+1)  (a) wherein n is from about 8 to about 100;

wherein m+p is from about 8 to about 100;

wherein q+r is from about 8 to about 100;

wherein s+t is from about 8 to about 100;

wherein u+v is from about 8 to about 100;

wherein w+x is from about 8 to about 100;

wherein y+z is from about 8 to about 100;

wherein e+f is from about 8 to about 100; or (i) a combination thereof.
 5. An ink according to claim 1 wherein the substituent is halogen, hydroxy, amino, imine, ammonium, pyridine, pyridinium, ether, aldehyde, ketone, ester, amide, carbonyl, thiocarbonyl, sulfate, sulfonate, sulfonic acid, sulfide, sulfoxide, phosphine, phosphonium, phosphate, phosphonate, nitrile, mercapto, nitro, nitroso, sulfone, acyl, acid anhydride, azide, azo, cyanato, isocyanato, thiocyanato, isothiocyanato, carboxylate, carboxylic acid, carbamate, carbamide, silyl, siloxyl, silane, or a combination thereof.
 6. An ink according to claim 1 wherein at least one of R₁ and R₂ has at least about 12 carbons.
 7. An ink according to claim 1 wherein R₆ and R₇ are joined to form an aromatic ring.
 8. An ink according to claim 1 wherein the colorant compound is present in the ink in an amount of at least about 0.1% by weight of the ink.
 9. An ink according to claim 1 wherein the colorant compound is present in the ink in an amount of no more than about 20% by weight of the ink.
 10. An ink according to claim 1 wherein the carrier comprises a branched triamide.
 11. An ink according to claim 10 wherein the branched triamide is of the formula

wherein x, y, and z each independently represent the number of propyleneoxy repeat units and x+y+z is from about 5 to about 6, and wherein p, q, and r are integers representing the number of repeat —(CH₂)— units, wherein p, q, and r each, independently of the others, are from about 34 to about
 40. 12. An ink according to claim 1 wherein the carrier comprises a urethane resin.
 13. An ink according to claim 1 wherein the carrier comprises a branched triamide, a monoamide, a polyethylene wax, and a urethane resin.
 14. An ink according to claim 1 wherein the carrier comprises an amorphous component and a crystalline component.
 15. A phase change ink composition comprising: (I) a phase change ink carrier; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 1 to about 100 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has in one embodiment at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; (c) R₃, R₄, R₅, R₆, and R₇ each, independently of the others, are: (1) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 1 to about 100 carbons; (2) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (3) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; (4) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; or (5) a substituent other than hydrogen, alkyl, aryl, arylalkyl, or alkylaryl which is halogen, hydroxy, amino, imine, ammonium, pyridine, pyridinium, ether, aldehyde, ketone, ester, amide, carbonyl, thiocarbonyl, sulfate, sulfonate, sulfonic acid, sulfide, sulfoxide, phosphine, phosphonium, phosphate, phosphonate, nitrile, mercapto, nitro, nitroso, sulfone, acyl, acid anhydride, azide, azo, cyanato, isocyanato, thiocyanato, isothiocyanato, carboxylate, carboxylic acid, carbamate, carbamide, silyl, siloxyl, silane, or a combination thereof; wherein two or more of R₃, R₄, R₅, R₆, and R₇ can be joined together to form a ring.
 16. An ink according to claim 15 wherein the colorant compound is of the formula


17. An ink according to claim 15 wherein the colorant compound is of the formula


18. An ink according to claim 15 wherein the carrier comprises a branched triamide.
 19. An ink according to claim 15 wherein the carrier comprises a triamide, a monoamide, a polyethylene wax, and a urethane resin.
 20. A phase change ink composition comprising: (I) a phase change ink carrier comprising a branched triamide, a monoamide, a polyethylene wax, and a urethane resin; and (II) a colorant compound of the formula

wherein: (a) R_(a) and R_(b) each, independently of the other, are: (i) hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, having from about 1 to about 100 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; and (b) R₁ and R₂ each, independently of the other, are: (i) hydrogen, provided that at least one of R₁ and R₂ is other than hydrogen; (ii) alkyl, including substituted and unsubstituted alkyl, wherein hetero atoms may optionally be present in alkyl, provided that when R₁ and R₂ are both alkyl at least one of R₁ and R₂ has in one embodiment at least about 6 carbons; (iii) aryl, including substituted and unsubstituted aryl, wherein hetero atoms may optionally be present in aryl, having from about 4 to about 24 carbons; (iv) arylalkyl, including substituted and unsubstituted arylalkyl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of arylalkyl, having from about 5 to about 100 carbons; or (v) alkylaryl, including substituted and unsubstituted alkylaryl, wherein hetero atoms may optionally be present in either the aryl or the alkyl portion of alkylaryl, having from about 5 to about 100 carbons; wherein at least one of R₁ and R₂ has at least about 12 carbons. 